Blue quinolin dye and process of making the same.



UNITED STATES PATENT BENNO HOMOLKA, or rRANKroRT-oN-THE-imri, GERM NY, ASSIGNOR TO FARBWERKE, .VORM. MEISTER Luoiosca BR-UNING,']OF1H(5CHST" ON-THE-MAIN, GERMANY, A con BLUE QUINQLIN DYE-AND PROCESS OFT- AKI G me-sime.

Specification of Letters Patent.

I Patented Feb. 1 9,-1'907.-

Applioat'ion filed lluiio l, 1905. Serial No. 819,668.. (Snecimanal 1'0 (11], whom it may OOTLCBIIL.

I Beit known thatl, BENNO HOMOLKA, Ph. D., chemist, a citizen of the Empire of Germany, residing at lirankforbon-the-Mam, Germany, have invented certain and useful Improvements in the Process of Making Blue Quinolin Dyes and Proces'sof Making the Same, of which the following is a specification. r to "By the action of alkalies on the salts ofcertain alkylammonium bases of the quinolinl facture of these newldyestufis, like water, v .65"

series Spalteholz obtained red dyestufi's (Berichte d. D. ,1,em.'Ges.,-XVI-, 1851) which- 3. 5 were further examined by Hoogewerff and 15. Von Dorp and called isocyaninesfwecueil des Travaux Ohimiguec des Payslg'as H1, 346.) Miethe and Book have cleared u i the constitution of these dyestuffs,(Be1', d. D.

Chem. (63., XXXVII, 2008,) while finally a series of homologues and substituted isocyanins became known by the United States Patent No. 805,143. I a

I have found that the salts of such alkylammonium bases of .the series of quinolins, or the salts of mixtures of such bases which by the action of alkalies yield isocyanins, may yield under other conditions blue oyestuff namely, if these salts be. 1 reated with alkalles in presence of forms liiehyde. If, for in- "3o stance, alkali be allowed to act on the alcoholic solution of a mixture of quinaldin-ethoiodid and qulnolin-etho-iozlid, a IBfl dyestufl may be obtained which Hoogewerff and Von Dorp (Z00. cit.) have called dicthyliso- 'cyanin, but if to the alcoholic solution of' the same mixture of quinolin-etho-iodid and quinalzlin-etho-iodid be first atldedformalzlehylc and final] y alkali, or the formalzlehyde simultancously with the alkali, then no 0 longer the rezl (liethylisocyanin, but anew beatifully blue (lyestuii is obtained. 1 call these new dyestull's cyanols, and have asccrtainczl that each isocyanin corresnonds with a cyanol. (Compare -E. Val'onta, Phoiogr. ('m-rcspondenz, XLHI Band, 3 Heft,

It in immaterial what salts of the alkylquinolinium and alkyl-quinalzlinium bases are cmployczl in the process just (lQSCI'lhGil.

- t Thesmnc result may be obtained by using lilU li:;i(is or sulfates, nitrates, &c., or even '1 the wi l of organic carbonicacids and sulfonic it is neither necessary to use readily a ms.

| prepared formaldehyde, ,assubstances may be used which produceformaltlehyde or are capable of'elim'inating formaldehyde -as,

lfor instance, methylal, anhydroform'alde' BOBATION or GERMANY};

l hytleanilin, &c. For t v e-alkali may be used; '7

i withthe same result the alkali-hydroxids, alkaline 'earth layer-oxide, and also certain different solvents-may be used in the manul ethyl alcohol, inethylalcohol, pyridin, &c.

' salts of alkaline reactionsuch,for instance,

as the alkali sulfit's. In vthe same manner i i The new. oyestutfs are not su.table for colorlstic' purposes as they" are not fast to of quinolin-etho-iodid and thirty, parts of quinaldin-etho-iorlid are dissolved in boiling alcohol. freshly-prepared mixture of thirty parts, by weight,ofcaustic-soialyeofsixtcenencent. strengths and twentyparts, by Weig t, of.for.

mal iehyde of forty-per-cent. strength. The

lQght; but they are. particularlysuitableffor Hilbel, Photograph. Cbrrespo nxl enz, XLIII i alcoholic so ution.-Thirty parts, by weight, r

To the. hot solution is added a liquid becomes of a deep blue within a few niinutes. Heating is continued on the waterbath for about one-half hour, whereupon it is allowed to cool, when the (lyestufi se al rates as beautiful crystals of a green meta lie 1 luster. These are filtered ofi, washed with l icy-cold alcohol, and recrystallized from boi i 'ing wood-spirit. The (lyestufl thus obtained 5 is soluble in alcohol, wood-spirit, and pyridin with a deep-blue color. Iii-water it is solui ble with (liiiiculty, the color of the aqueous l solution being of a decided redder him than 3 that of the alcoholic solution. The aqueous and alcoholic solutions are not decolorize'zl by carbonic acid; but an excess of acetic acid prorluces decolorization. Dilute mineral l acids even have to be add ed in considerablev quantities in order to (lccolorize the solutions.

l Example I I Dy es tufi' from qui nolin-metho-v chloral and meta orpara-tolv1quinalclimethm iod'id obtained in'aqueous solution.-Twentyiivcparts of quiuolin-met.hachlorid and thirty parts, by weigh t, of toluquinaldin-etho- 3o recrystallized froini alcohol 'or wood-spirit.

iodid are dissolved together in five hundred parts, byi-weighh-of ho,t'\water. To tlL's solution are aidoei eighteen fparts,by: weight, of r forn aldehyde ofvforty perscent. strength and then twenty-fiyeparts byweight of causticsoia lye of sixteen-percent. strength. The wholeis heated fora short time, whereupon cthed estufl' separates in form of crusts of y fme'tal iefl-uster. These are separated from in the aqueous solution and recrystallized from alcohol orlwood spirit." The -cyestufl is soluble in alcohol,-'soluble with difliculty in water with'a-green blueicolor, and has the same -@nsertgesfas-thataboye described. ;1 5- i 1 sample FIZZ-+Dyestafl' from g uin aldin- ---?etho-'i0d-id obtained in pyridin soZution.- #:Thirty? parts, by weight, of quinalJin-ethoiozlid are dissolved in one-huncred and fifty partafby'wei'ght, o'f hot pyridin. To the hot soluti'iin are aiceil ten parts, by weight, of r'mal- "ehyde of forty-per cent. strength and tentdlifceen parts, by weight, of caustic-soda -,:lyeiof'snrteemper-cent, strength, whereupon ,thewhole is heated to bo' ling for a few min- 5 -utes. "*VVhen cold, the dyestull' separates artly as crystals of'metall'ic luster. It is diluted-with about five hundred parts, by I weight, of water, the now entirely separated 'dyestufi is filtered, washed with'water, and

The 'dyestufi is soluble in alcohol with a blue color and has the-same properties as that described before.

In the above examples maybe substituted: 1; For the salts mentionei'therein of the -alkyl-quinal3inium and alkyl-qulnolinium bases the salts of homologous 'and'substituted alky -qunaliinium and alkyl-quinolinium bases. The dyestulls thus obtained-are 4o. all ..blue, green-blue to blue-green, and have the same properties asthose abovedescribed.

J 2. For the formaldehyde such compounds monia.

as readily eliminate formaldehyde or may be easly transformed into formaldehyde, for instance, anhydroformalzlehyde anilin and its 5 homologues, xnethylal, .ethylaliand the like.

Bysusing these bodies the processis not essentially changed. v

3. For the caustic-soda. lye equivalent quantity of caustic potash or other alkali- 5o hydroxlds," alkaline earths hydroxide and galts of alkaline reaction, such as alkali sultes.

Having now described my invention, what I claim is 4 v i 1. The herein-described process of making blue basic dyestuffs of the (ulnolin series, which consists in reactin wit certain inor ganie compounds ofalkaline reaction herein -.escribed 1n presence of formaldehyde on s0 6 c lutions of salts of such alkylammonium bases of the quinolin series-as yleld-isocyanins by the action'of alkalies.

2. As new product, the dyestuff obtained by the action of certain inorganic substances of alkaline reaction in presence of formaldehyde on solution'sof salts of'alkylammonium bases of the quinolin series which by the action of alkal-ies yield iso'eyanins, .said dyestuff being excessively sensitive to light and insoluble 1n ether, benzene, toluene, xylene 'anl ligroine, soluble with a blue color 1n alcohol, methyl alcohol, 'a'ceton and chlorofor'rn, soluble in water with a violetcolor;

' the aqueoussolution is-decolorizei by'min- 4 era-1 acids and restoredbyalkalies and am- In testimon ithat'I claim the foregoing as my invention 1 have signed my-name m-ptes ence of two subscribing witnesses.

BENNO-HQMOLKA. Witnessesa. v,

JEAN GRUND',

CARL -GRUND. 

